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Publication numberUS4684709 A
Publication typeGrant
Application numberUS 06/833,939
Publication dateAug 4, 1987
Filing dateFeb 25, 1986
Priority dateFeb 28, 1985
Fee statusPaid
Also published asCA1261528A1, EP0193402A2, EP0193402A3
Publication number06833939, 833939, US 4684709 A, US 4684709A, US-A-4684709, US4684709 A, US4684709A
InventorsIsao Ona, Masaru Ozaki, Tadashi Fujii
Original AssigneeToray Silicone Co., Ltd.
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Organopolysiloxane compounds comprising epoxy-terminated polyoxyalkylene radicals
US 4684709 A
Abstract
Organopolysiloxane compounds containing at least one silicon-bonded, epoxy-terminated polyoxyalkylene group are useful for treating materials to provide hydrophilicity for the materials.
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Claims(6)
That which is claimed is:
1. An organopolysiloxane compound having the formula
AR2 SiO(R2 SiO)x (RQSiO)y SiR2 A
wherein R is a monovalent hydrocarbon or halogenated hydrocarbon group having from 1 to 10 carbon atoms, A is R or Q, Q is a group with the formula ##STR20## R1 is an alkylene group having from 3 to 5 carbon atoms, a has an average value of 0 to 30, b has an average value of 0 to 30, a+b has an average value of 2 to 60, x has an average value of 1 to 500, y has an average value of 0 to 100, and containing at least one Q group in each molecule.
2. An organopolysiloxane compound in accordance with claim 1 wherein R is methyl.
3. An organopolysiloxane compound in accordance with claim 2 wherein both A groups are methyl and y has a value of at least 1.
4. An organopolysiloxane compound in accordance with claim 2 wherein both A groups are Q groups.
5. An organopolysiloxane compound in accordance with claim 4 wherein y has a value of at least 1.
6. An organopolysiloxane compound in accordance with claim 1 wherein a+b has an average value of at least 3.
Description
BACKGROUND OF THE INVENTION

The present invention describes novel organopolysiloxane compounds. More specifically, the present invention describes novel organopolysiloxane compounds wherein each molecule has at least 1 silicon-bonded polyoxyalkylene group having a terminal epoxy group.

Organopolysiloxanes have an extremely wide range of properties, such as those of an oil, rubber or solid resin, depending on the composition, size and form of the basic structure, on the type of side chains in the basic structure, on the molecular weight, etc. They are used in a number of diverse industrial fields such as textiles, release paper, electrical fields, electronics, construction and paint additives, etc., due to their characteristic heat resistance, cold resistance, oxidation stability, weather resistance, lubrication, water repellency and insulation.

Organopolysiloxanes with polyoxyalkylene or epoxy groups in each molecule are well known from Japanes Patents Nos. 53-8360 [78-8360] and 51-33839 [76-33839]. In addition, organopolysiloxanes with both polyoxyalkylene and epoxy groups in each molecule are also well known from Japanese Kokai [Laid Open] Pat. No. 49-75897 [74-75897].

However, organopolysiloxanes are heretofore unknown which contain in each molecule a polyoxyalkylene group with a terminal epoxy group.

BRIEF SUMMARY OF THE INVENTION

The goal of the present invention is to provide novel, useful organopolysiloxane compounds wherein each molecule contains at least 1 polyoxyalkylene group with a terminal epoxy group. This goal is accomplished by organopolysiloxane compounds having the formula AR2 SiO(R2 SiO)x ((RQSiO)y SiR2 A wherein R is a monovalent hydrocarbon or halogenated hydrocarbon group having from 1 to 10 carbon atoms, A is R or Q, Q is a group with the formula ##STR1## R1 is an alkylene group having from 3 to 5 carbon atoms, a has an average value of 0 to 30, b has an average value of 0 to 30, a+b has an average value of 2 to 60, x has an average value of 1 to 500 and y has an average value of 0 to 100 and containing at least 1 Q group in each molecule.

DETAILED DESCRIPTION OF THE INVENTION

By way of explanation, in the preceding formulas, R is a C1 to C10 monovalent hydrocarbon or halogenated hydrocarbon group and concrete examples thereof are alkyl groups such as methyl, ethyl, propyl and octyl; aralkyl groups such as 2-phenylethyl and 2-phenylpropyl; aryl groups such as phenyl and tolyl and halogenated derivatives thereof such as 3,3,3-trifluoropropyl. The R groups within a single molecule may be identical or different.

Herein R1 is a C3 to C5 alkylene group and concrete examples thereof are --CH2 CH2 CH2 --, --CH(CH3)Ch2 --, --(CH2)4 --, --CH2 CH(CH3)CH2 --, --(CH2)5 -- and --CH2 C(CH3)2 --. The R1 groups within a single molecule may be identical or different.

The Q group has the formula ##STR2##

This group provides the organopolysiloxane compounds of the present invention with the reactivity of the epoxy group, which is reactive with various substrates and various resins, and with the hydrophilicity, antistaticity, miscibility with organic resins and paintability of the polyoxyalkylene group.

In Q a has an average value of from 0 to 30, b has an average value of from 0 to 30 and a+b has an average value of from 2 to 60.

The endgroups (A) are R and/or Q the A groups may be identical or different. However, at least 1 Q group must be present in each molecule.

Said organopolysiloxanes are novel compounds which are heretofore unreported in the literature and concrete examples thereof are ##STR3##

The synthesis of the organopolysiloxane compounds of the present invention is exemplified in the following, well-known synthesis routes.

For the case of A=R, the organopolysiloxane of the present invention is synthesized, for example, by the addition reaction of an organohydrogenpolysiloxane with the general formula R3 SiO(R2 SiO)y SiR3, wherein R, x and y are all defined as above, with a polyoxyalkylene containing alkenyl and epoxy groups with the general formula ##STR4## wherein R, a and b are all defined as above, and R2 is a C3 to C5 alkenyl group, in the presence of a platinum-type catalyst such as chloroplatinic acid.

The polyoxyalkylene with a terminal epoxy and a terminal alkenyl group can be produced by, for example, the addition reaction of an alkenyl alcohol with the general formula R2 OH, wherein R2 is defined as above, with a moles ethylene oxide and b moles propylene oxide to produce an alkenyl group-containing polyoxyalkylene with the general formula R2 (C2 H4 O)a (C3 H6 O)b H wherein R2, a and b are all defined as above, which is then reacted with epichlorohydrin with dehydrochlorination. Polyoxyalkylene with a terminal epoxy group and a terminal alkenyl group and with the general formula ##STR5## is thus produced.

For the case of A=Q, the organopolysiloxane compound of the present invention may be synthesized, for example, by the addition reaction of an organohydrogensiloxane with the general formula HR2 SiO(R2 SiO)x SiR2 H wherein R and x are defined as above, or an organohydrogenpolysiloxane with the general formula HR2 SiO(R2 SiO)x (RHSiO)y SiR2 H with the above-mentioned polyoxyalkylene with a terminal epoxy group and a terminal alkenyl group in the presence of a platinum-type catalyst such as chloroplatinic acid.

The above-mentioned organohydrogenpolysiloxanes may be synthesized by the polymerization of suitable quantities of organodisiloxane with the general formula R3 SiOSiR3, organohydrogendisiloxane with the general formula HR2 SiOSiR2 H, cyclic organohydrogenpolysiloxane with the general formula ##STR6## and cyclic organopolysiloxane with the general formula ##STR7## wherein n is an integer of 3 to 10, in the presence of an acid catalyst such as sulfuric acid, nitric acid, trifluoromethanesulfonic acid or activated clay.

The organopolysiloxanes of the present invention are novel compounds which contain a polyoxyalkylene group with a terminal epoxy group. They have the reactivity of the epoxy group and the hydrophilicity, antistaticity, miscibility with organic resins and paintability of the polyoxyalkylene group.

Due to this, the organopolysiloxanes of the present invention are appropriately employed as treatment agents for solids such as various fibers and their knits and weaves; sheet materials such as paper, natural and synthetic leathers, cellophane and plastic films; foams such as synthetic resin foams; synthetic resin moldings; natural and synthetic rubber moldings; metal moldings; glass moldings; and powdery materials such as inorganic powders and synthetic resin powders. They are also appropriately employed as additives to various resins and rubbers such as organic resins, organic rubbers, organic elastomers as well as organopolysiloxane resins, organopolysiloxane rubbers and organopolysiloxane elastomers.

The present invention will be illustrated, but not limited, using examples of execution. "Parts" in the examples means "weight parts" and the viscosity and refractive index are the values measured at 25 C. Me means methyl. Ph means phenyl. cS means centistokes.

EXAMPLE 1

Ten and five-tenths part hexamethyldisiloxane, 262.5 parts cyclic dimethylpolysiloxane tetramer, 27.0 parts trimethylsilyl-terminated methylhydrogenpolysiloxane with a viscosity of 21 cS and 3 parts of an adequately dried activated clay as the polymerization catalyst are all charged to a three-neck flask equipped with a stirrer, reflux condenser and thermometer and polymerized at 70 C. for 8 hours and then filtered with a filtering aid to obtain a trimethylsilyl-terminated dimethylsiloxane-methylhydrogensiloxane copolymer with a viscosity of 60 cS and with the formula Me3 SiO(Me2 SiO)55 (MeHSiO)7 SiMe3.

Sixty-seven and four-tenths parts of this trimethylsilyl-terminated dimethylsiloxane-methylhydrogensiloxane copolymer, 32.6 parts of a polyoxyalkylene with a terminal allyl group and a terminal epoxy group and with the formula ##STR8## and 25 parts toluene are all charged to a three-neck flask equipped with a stirrer, reflux condenser and thermometer and heated to 85 C. One-tenth part of 3 weight percent isopropanolic chloroplatinic acid is then added and this is then reacted at 120 C. for 3 hours. The toluene and low volatiles are stripped at 140 C./20 mm Hg to obtain an oil with a viscosity of 440 cS, a refractive index of 1.4323 and an epoxy group content of 4.3 weight percent.

The product is confirmed to be an organopolysiloxane with the formula ##STR9## according to infrared absorption spectral analysis (Spectrum 1), nuclear magnetic resonance spectral analysis (Spectrum 2) and the above-mentioned analytic results.

EXAMPLE 2

Sixty-seven and two-tenths parts tetramethyldisiloxane, 742 parts cyclic dimethylpolysiloxane tetramer, 60.1 parts cyclic methylhydrogenpolysiloxane and 10 parts of an adequately dried activated clay as the polymerization catalyst are all charged to a three-neck flask equipped with a stirrer, reflux condenser and thermometer, polymerized at 55 C. for 10 hours and then filtered with a filtering aid to obtain a dimethylhydrogensilyl-terminated dimethylsiloxane-methylhydrogensiloxane copolymer with a viscosity of 13 cS and with the formula HMe2 SiO(Me2 SiO)20 (MeHSiO)2 SiMe2 H.

Forty-one and six-tenths parts of this dimethylhydrogensilyl-terminated dimethylsiloxane-methylhydrogensiloxane copolymer, 58.4 parts of a polyoxyalkylene with a terminal allyl group and a terminal epoxy group and with the formula ##STR10## and 20 parts toluene are all charged to a three-neck flask equipped with a stirrer, reflux condenser and thermometer, heated at 110 C., 0.1 part of 3 weight percent isopropanolic chloroplatinic acid is added and this is then reacted at 120 C. for 2 hours. The toluene and low volatiles are stripped at 140 C./20 mm Hg to obtain an oil with a viscosity of 600 cS, a refractive index of 1.4470 and an epoxy group content of 5.1 weight percent. The product is confirmed to be an organopolysiloxane with the formula ##STR11## according to infrared absorption spectral analysis (Spectrum 3), nuclear magnetic resonance spectral analysis (Spectrum 4) and the preceding analytic results.

EXAMPLE 3

Eleven and four-tenths parts tetramethyldisiloxane, 88.6 parts cyclic dimethylpolysiloxane tetramer and 3 parts adequately dried activated clay as the polymerization catalyst were all charged to a three-neck flask equipped with a stirrer, reflux condenser and a thermometer, polymerized at 55 C. for 10 hours and then filtered with a filtering aid to obtain dimethylhydrogensilyl-terminated dimethylpolysiloxane with a viscosity of 9 cS and with the formula HMe2 SiO(Me2 SiO)14 SiMe2 H.

Forty-eight and nine-tenths parts of this dimethylhydrogensilyl-terminated dimethylpolysiloxane, 51.1 parts of a polyoxyalkylene with a terminal allyl group and a terminal epoxy group and with the formula ##STR12## and 30 parts toluene are all charged to a three-neck flask equipped with a stirrer, reflux condenser and a thermometer, heated to 80 C., 0.1 part 3 weight percent isopropanolic chloroplatinic acid is added and this is then reacted at 110 C. for 2 hours. The toluene and low volatiles are stripped at 140 C./20 mm Hg to provide an oil with a viscosity of 255 cS, a refractive index of 1.4410 and an epoxy group content of 3.9 weight percent.

The product is confirmed to be an organopolysiloxane with the formula ##STR13## according to infrared absorption spectral analysis (Spectrum 5), nuclear magnetic resonance spectral analysis (Spectrum 6) and the analytic results above.

EXAMPLE 4

Sixty-nine and six-tenths of the same trimethylsilyl-terminated dimethylsiloxane-methylhydrogensiloxane copolymer as in example 1, 30.4 parts of a polyoxyalkylene with a terminal allyl group and a terminal epoxy group and with the formula ##STR14## and 25 parts toluene are all charged to a three-neck flask equipped with a stirrer, reflux condenser and a thermometer, heated to 85 C., 0.1 part 3 weight percent isopropanolic chloroplatinic acid is added and this is then reacted at 120 C. for 3 hours. The toluene and low volatiles are stripped at 140 C./20 mm Hg.

The resulting liquid has a viscosity of 170 cS, a refractive index of 1.4170 and an epoxy group content of 4.3 weight percent and is confirmed to be an organopolysiloxane with the formula ##STR15## according to infrared absorption spectral analysis (Spectrum 7) and nuclear magnetic resonance spectral analysis (Spectrum 8).

EXAMPLE 5

Twenty-five and two-tenths parts of a trimethylsilyl-terminated dimethylsiloxane-methylhydrogensiloxane copolymer with the formula Me3 SiO(Me2 SiO)130 (MeHSiO)10 SiMe3, 74.8 parts of a polyoxyalkylene with a terminal allyl group and a terminal epoxy group and with the formula ##STR16## and 25 parts toluene are all charged to a three-neck flask equipped with a stirrer, reflux condenser and a thermometer, heated to 85 C., 0.1 part 3 weight percent isopropanolic chloroplatinic acid is added and this is then reacted at 120 C. for 3 hours. The toluene and low volatiles are stripped at 140 C./20 mm Hg to obtain a liquid with a viscosity of 3500 cS, a refractive index of 1.4408 and an epoxy group content of 1.2 weight percent. This is confirmed to be an organopolysiloxane with the formula ##STR17## according to infrared absorption spectral analysis (Spectrum 9), nuclear magnetic resonance spectral analysis (Spectrum 10) and the above-mentioned analytic results.

EXAMPLE 6

Sixty-eight and five-tenths parts of an organopolysiloxane with the formula

PhC2 H4 Me2 SiO(Me2 SiO)8 (MeHSiO)2 Me2 SiC2 H4 Ph

31.5 parts of polyoxyalkylene with a terminal allyl group and a terminal epoxy group and with the formula ##STR18## and 25 parts toluene are all charged to a three-neck flask equipped with a stirrer, a reflux condenser and a thermometer, heated to 85 C., 0.1 part 3 weight percent isopropanolic chloroplatinic acid is added and this is then reacted at 120 C. for 3 hours. The toluene and low volatiles are stripped at 140 C./20 mm Hg to obtain a liquid with a viscosity of 80 cS, a refractive index of 1.4495 and an epoxy group content of 5.8 weight percent. This is confirmed to be an organopolysiloxane with the formula ##STR19## according to infrared absorption spectral analysis, nuclear magnetic resonance spectral analysis and the above-mentioned analytic results.

SIMPLE EXPLANATION OF THE FIGURES

FIGS. 1, 3, 5, 7 and 9 show the results for the infrared absorption spectral analyses of the products produced in Examples 1, 2, 3, 4, and 5, respectively.

FIGS. 2, 4, 6, 8, and 10 show the results for the nuclear magnetic resonance spectral analyses of the products produced in Examples 1, 2, 3, 4 and 5, respectively.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US4208503 *Sep 18, 1978Jun 17, 1980Sws Silicones CorporationEpoxy-functional polysiloxane polymers
US4490416 *May 15, 1984Dec 25, 1984Dow Corning LimitedFilms of cured polyethersiloxane copolymers modified by an epoxy-containing silane
EP0157218A1 *Mar 8, 1985Oct 9, 1985Daikin Industries, LimitedFluorine-containing silane compounds and method of preparing them
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4822687 *Jan 22, 1988Apr 18, 1989Minnesota Mining And Manufacturing CompanySilicone release compositions
US4906465 *Mar 16, 1988Mar 6, 1990Massachusetts Institute Of TechnologyAntithrombogenic devices containing polysiloxanes
US4910015 *Oct 19, 1987Mar 20, 1990Massachusetts Institute Of TechnologySurface-active polysiloxanes and drug releasing materials thereof
US4987203 *Oct 24, 1989Jan 22, 1991Chisso CorporationPolyorganosiloxane compounds with epoxy group
US5178959 *Mar 27, 1991Jan 12, 1993General Electric CompanyEpoxy-functional fluorosilicones
US5217805 *Oct 15, 1991Jun 8, 1993Minnesota Mining And Manufacturing CompanyRelease lining, adhesive tape
US5232959 *May 22, 1991Aug 3, 1993Dow Corning Toray Silicone Co., Ltd.Organohydrogenpolysiloxanes and curable organosiloxane compositions containing same
US5408012 *May 27, 1993Apr 18, 1995Comfort Technologies, Inc.Polyester or polyamide bonding with reaction product of primary hydroxylate and a silane without polymerizing
US5807956 *Mar 4, 1997Sep 15, 1998Osi Specialties, Inc.Silicone aminopolyalkyleneoxide block copolymers
US5981681 *Jun 17, 1998Nov 9, 1999Witco CorporationSilicone aminopolyalkyleneoxide block copolymers
US8158716 *Jul 16, 2009Apr 17, 2012Shin-Etsu Chemical Co., Ltd.Preparation of hydrolyzable group-containing organohydrogenpolysiloxane and organopolysiloxane derived therefrom
Classifications
U.S. Classification528/15, 556/457, 556/445, 556/479, 556/458, 528/31, 528/27
International ClassificationC08L83/06, C08G59/32, C08L83/04, C09D183/06, C08G77/46, C08G77/14, C09D183/04, C08G77/22, C08G77/38, C08G59/00, C08G77/00, C08L63/00
Cooperative ClassificationC08G77/38, C08G77/46
European ClassificationC08G77/46, C08G77/38
Legal Events
DateCodeEventDescription
Jan 20, 1999FPAYFee payment
Year of fee payment: 12
Dec 5, 1994FPAYFee payment
Year of fee payment: 8
Dec 6, 1990FPAYFee payment
Year of fee payment: 4
Dec 29, 1986ASAssignment
Owner name: TORAY SILICONE COMPANY, LTD., 2-8 MUROMACHI NIHONB
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:ONA, ISAO;OZAKI, MASARU;FUJII, TADASHI;REEL/FRAME:004648/0945
Effective date: 19860421
Owner name: TORAY SILICONE COMPANY, LTD.,JAPAN
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ONA, ISAO;OZAKI, MASARU;FUJII, TADASHI;US-ASSIGNMENT DATABASE UPDATED:20100526;REEL/FRAME:4648/945
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ONA, ISAO;OZAKI, MASARU;FUJII, TADASHI;REEL/FRAME:004648/0945